WO2018047681A1 - Nouveau composé, composition, matériau photochromique et agent de contrôle de propriété photo-interfaciale - Google Patents

Nouveau composé, composition, matériau photochromique et agent de contrôle de propriété photo-interfaciale Download PDF

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WO2018047681A1
WO2018047681A1 PCT/JP2017/030994 JP2017030994W WO2018047681A1 WO 2018047681 A1 WO2018047681 A1 WO 2018047681A1 JP 2017030994 W JP2017030994 W JP 2017030994W WO 2018047681 A1 WO2018047681 A1 WO 2018047681A1
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group
compound according
substituent
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integer
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酒井　秀樹
酒井　健一
好司 土屋
允顕 赤松
大輝 鈴木
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学校法人東京理科大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/88—Nitrogen atoms, e.g. allantoin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials

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  • the present invention relates to a novel compound, composition, photochromic material, and interfacial physical property light control agent.
  • Photochromic materials that have the function of changing optical properties (color (transmittance of visible light), fluorescence, etc.) by irradiating light such as visible light and ultraviolet light are glasses for preventing glare, optical switches, or Used as a display material such as ink having a display / non-display switching function.
  • applications as recording materials such as optical disks and holograms are also being studied.
  • the color change due to the photochromic material is manifested by a reversible chemical change of the photochromic compound by light irradiation.
  • the color change caused by the light irradiation is called a dimming function.
  • Typical photochromic compounds include spiropyran compounds, spirooxazine compounds, naphthopyran compounds, fulgide compounds, diarylethene compounds, and the like, which have been used in various applications.
  • the light control function requires characteristics such as color, color density and color development speed suitable for the application, various derivatives and compounds having new molecular skeletons are being developed.
  • a surfactant is used in order to control physical properties of the interface.
  • the surfactant forms various molecular aggregates such as micelles, string-like micelles, vesicles, and emulsions in an aqueous solution.
  • the form in which a molecule forms an aggregate depends on its geometrical shape, hydrophilicity / hydrophobicity balance, and the like. Needless to say, the formation of these molecular aggregates is greatly related to the expression of functions such as washing, solubilization and dispersion of the surfactant.
  • Examples of interfacial physical property control using a surfactant include control of the release of drugs or fragrances in cosmetics and the like, control of the drying speed of ink, and the like.
  • Patent Document 1 describes a compound represented by the following general formula (1) as a photochromic compound.
  • R A and R B are a linear or branched alkyl group, alkylamino group and a C 2-20 linear or branched group having 1 to 20 carbon atoms.
  • k, l, m, and n are each independently an integer of 1 to 5)
  • Patent Document 2 describes a compound having a hexaarylbisimidazole structure as a photopolymerization initiator.
  • the problem to be solved by the present invention is to provide a novel compound having a hexaarylbisimidazole structure.
  • Another problem to be solved by the present invention is to provide a composition, a photochromic material, or an interfacial property control agent containing the novel compound.
  • ⁇ 1> having a hexaarylbisimidazole structure A compound having at least one functional group having a hydrophilic group in at least one aromatic ring bonded to the imidazole ring of the hexaarylbisimidazole structure.
  • ⁇ 2> having a hexaarylbisimidazole structure A compound having at least one functional group having a hydrophilic group in at least one aromatic ring bonded to the 2-position of the imidazole ring of the hexaarylbisimidazole structure.
  • ⁇ 3> The compound according to ⁇ 2>, wherein the aromatic group bonded to the 2-position of each imidazole ring in the hexaarylbisimidazole structure has a functional group having the hydrophilic group.
  • ⁇ 4> The compound according to any one of ⁇ 1> to ⁇ 3>, wherein the hydrophilic group is an ionic group or a nonionic group.
  • ⁇ 5> The compound according to ⁇ 4>, wherein the ionic group is a cationic group or an anionic group.
  • ⁇ 6> The compound according to any one of ⁇ 1> to ⁇ 5>, which is a compound represented by the following formula (1).
  • R ion independently represents an ionic group
  • L independently represents a single bond or a divalent linking group
  • X ion independently represents a counter ion
  • R 1 And R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a linear or branched alkyl group which may have a substituent, or a cycloalkyl which may have a substituent.
  • ⁇ 7> The compound according to ⁇ 6>, wherein at least one of the R ions is a cationic group.
  • ⁇ 8> The compound according to ⁇ 7>, wherein the cationic group is a quaternary ammonium group.
  • ⁇ 9> The compound according to ⁇ 6>, wherein at least one of the R ions is an anionic group.
  • ⁇ 10> The compound according to ⁇ 9>, wherein the anionic group is a carboxylate group.
  • ⁇ 11> The compound according to any one of ⁇ 6> to ⁇ 10>, wherein all of p are 1.
  • ⁇ 12> The compound according to any one of ⁇ 1> to ⁇ 5>, which is a compound represented by the following formula (5).
  • R no independently represents a group having a nonionic hydrophilic group
  • R n1 and R n2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a substituent.
  • Linear or branched alkyl group which may have, cycloalkyl group which may have substituent, linear or branched alkenyl group which may have substituent, substituent
  • a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, a linear or branched alkyloxy group which may have a substituent, a substituted or unsubstituted aryl
  • np independently represents an integer of 0 to 5; the sum of two np is 1 or more;
  • np + nq in np and nq represents the number of groups bonded to one benzene ring is an integer of 1 ⁇ 5
  • nr each independently represents an integer of 0-5.
  • ⁇ 13> The compound according to ⁇ 12>, wherein R no is a group having a polyalkyleneoxy structure.
  • R no is a group having a polyalkyleneoxy structure.
  • a composition comprising the compound according to any one of ⁇ 1> to ⁇ 13> and an aqueous medium.
  • a photochromic material comprising the compound according to any one of ⁇ 1> to ⁇ 13>.
  • An interfacial physical property light control agent comprising the compound according to any one of ⁇ 1> to ⁇ 13>.
  • a novel compound having a hexaarylbisimidazole structure can be provided.
  • the composition, photochromic material, or interface physical property control agent containing the said novel compound can be provided.
  • the vertical axis represents the absorbance
  • the horizontal axis represents the wavelength (unit: nm).
  • Dark indicates a state in which no ultraviolet rays are irradiated
  • UV indicates a state in which the ultraviolet rays are irradiated.
  • the vertical axis represents the absorbance (Abs @ 620 nm) of light having a wavelength of 620 nm
  • the horizontal axis represents time (unit: s (seconds)).
  • the compound according to this embodiment has a hexaarylbisimidazole structure, and has at least one functional group having a hydrophilic group in at least one aromatic ring bonded to the imidazole ring of the hexaarylbisimidazole structure.
  • the compound according to the present embodiment has a hexaarylbisimidazole structure from the viewpoint of surface activity and the formation of molecular aggregates such as micelles, and the 2-position of the imidazole ring of the hexaarylbisimidazole structure. It is preferable to have at least one functional group having a hydrophilic group in at least one aromatic ring bonded to the.
  • the compound according to the present embodiment has a functional group having the hydrophilic group from the viewpoint of surface activity and the formation of a molecular aggregate such as a micelle. More preferably, the aromatic ring is bonded to the 2-position.
  • the compound according to the present embodiment is a novel compound having a hexaarylbisimidazole structure, and is a compound that can form a precise and regular structure (for example, a molecular assembly such as a micelle) capable of controlling surface activity. is there.
  • the compound according to the present embodiment includes a hydrophilic group or a group having a hydrophilic group bonded to the aromatic ring bonded to the 2-position of each imidazole ring in the hexaarylbisimidazole structure (also referred to as a lophine dimer structure).
  • each By having each, it shows water solubility or oil solubility (especially water solubility different from a normal lophine dimer), and shows reversible structural change accompanying ultraviolet light (also referred to as UV) irradiation, that is, photochromism. It is visually confirmed as a color change. Furthermore, it is possible to control interface physical properties such as viscosity and thermal stability accompanying the change in micelle structure.
  • the compound according to the present embodiment has amphiphilic properties due to the above-described configuration, it depends on the structure of each part in the compound, etc., but is self-organized in micellar or the like in an aqueous medium such as water. In addition, in a non-polar solvent, it is self-assembled to form a molecular assembly such as a reverse micelle.
  • the radical generated by the cleavage of the bond connecting two imidazole rings with ultraviolet light irradiation also referred to as the lophyl radical
  • the recombination rate was higher than that in a normal lophine dimer in an organic solvent.
  • the recombination reaction is caused by a thermal reaction, but in the compound according to this embodiment, the generated lophyl radical is recombined even at room temperature (25 ° C.).
  • the compound has a group in which an ammonium group is bonded as a hydrophilic group on an aromatic ring bonded to the 2-position of each imidazole ring in the hexaarylbisimidazole structure.
  • a bond connecting two imidazole rings is cleaved to generate two lophine radicals.
  • the time from the irradiation of the ultraviolet rays to the generation of the loffin radical is short, and visually, a color change derived from the loffin radical occurs immediately after the irradiation of the ultraviolet light.
  • the ultraviolet irradiation when the ultraviolet irradiation is stopped at room temperature (25 ° C.), the compound undergoes a recombination reaction, and the two lophine radicals recombine with the original compound. Visually, the color can be erased almost simultaneously with the stop of irradiation with ultraviolet light (decoloration reaction).
  • the compound has a group in which an ammonium group is bonded as a hydrophilic group on the aromatic ring bonded to the 2-position of each imidazole ring, the vicinity of the ammonium group is a hydrophilic group, and the hexaarylbis
  • the imidazole structure and the linking group moiety function as a hydrophobic group, have surface activity, and exhibit interface properties in an aqueous medium, as shown below, and molecular aggregates such as micelles and vesicles (hereinafter referred to as micelles). Formed).
  • the molecular structure of the compound according to the present embodiment changes greatly when the lophyl radical is generated by irradiation with ultraviolet light. Therefore, depending on the position and structure of the substituent, the composition of the aqueous solution, etc., the molecular assembly ( A change in the shape of micelles) is also induced, and the interface physical properties can be controlled by light.
  • the interface physical properties can be controlled by light.
  • an aspect in which the change in the micelle form is small as schematically shown in the upper part of the following, or an aspect in which the change of the micelle form is large as schematically shown in the lower part of the following is appropriately selected. It becomes possible to design. Control of the interface physical properties due to such a change in micelle morphology can be switched with light (ultraviolet rays).
  • the compound according to this embodiment preferably has at least one hydrophilic group, and has two or more from the viewpoints of surface activity and formability of molecular aggregates such as micelles.
  • the hydrophilic group is preferably an ionic group or a nonionic group.
  • the ionic group include a cationic group, an anionic group, and a zwitterionic group.
  • a cationic group or a zwitterionic group is preferable, and a cationic group is more preferable.
  • an anionic group or a zwitterionic group is preferable, and an anionic group is more preferable.
  • Examples of the cationic group include groups containing a nitrogen atom and the like, primary to quaternary ammonium groups, pyridinium groups, and imidazolium groups are preferable, and quaternary ammonium groups are particularly preferable.
  • Examples of the anionic group include a carboxylate group, a sulfonate group, a phosphonate group, and a sulfate anion group (sulfate group), a carboxylate group and a sulfonate group are more preferable, and a sulfonate group is particularly preferable.
  • a betaine structure is preferably exemplified.
  • the combination of the cationic structure and the anionic structure in the betaine structure is preferably a combination of the cationic group and the anionic group.
  • a betaine structure in which a quaternary ammonium group and a carboxylate group or a sulfonate group are combined is particularly preferable.
  • An example of a betaine structure is —N + (R B ) 2 —L B —CO 2 — .
  • R B each independently represent an alkyl group having 1 to 4 carbon atoms
  • L B represents an alkylene group having 1 to 8 carbon atoms.
  • the nonionic hydrophilic group is preferably a hydrophilic group in a nonionic surfactant, a group having a polyalkyleneoxy structure, two or more hydroxy groups, and More preferred are a group having an ester structure and a group having an alkanolamide structure.
  • the polyalkyleneoxy structure in the group having a polyalkyleneoxy structure preferably includes a polyethyleneoxy structure, a polypropyleneoxy structure, and a poly (ethyleneoxy / propyleneoxy) structure in which these are mixed, and more preferably a polyethyleneoxy structure. .
  • the repeating number of the alkyleneoxy structure in the polyalkyleneoxy structure may be 2 or more, more preferably 2 to 10, and particularly preferably 3 to 8.
  • one terminal of the group having a polyalkyleneoxy structure is preferably an alkoxy group or a hydroxy group, more preferably an alkoxy group, and particularly preferably a methoxy group or an ethoxy group.
  • Preferred examples of the group having two or more hydroxy groups and an ester structure include a group having a glycerin monoester structure, a group having a sorbitan ester structure, and a group having a sucrose ester structure.
  • Preferred examples of the group having an alkanolamide structure include a group having a diethanolamide structure.
  • the compound according to this embodiment preferably has a counter ion that electrically neutralizes the hydrophilic group.
  • the hydrophilic group is a zwitterionic group such as a betaine structure, it may not have a counter ion.
  • the counter ion is not particularly limited as long as it is electrically neutralized as a whole compound, and it may be an anion, a cation, a monovalent ion, a divalent or higher valent ion.
  • the number of counter ions may be one or two or more, but from the viewpoint of solubility in an aqueous medium, it is preferably a monovalent ion.
  • the counter ion is preferably Cl ⁇ , Br ⁇ , BF 4 ⁇ , or PF 6 ⁇ from the viewpoint of solubility in an aqueous medium, and Cl ⁇ . or, Br - it is more preferable.
  • the counter ion is preferably an alkali metal ion, an alkaline earth metal ion or a quaternary ammonium ion from the viewpoint of solubility in an aqueous medium. More preferably, it is an ion.
  • the number of hydrophilic groups possessed by the compound according to this embodiment is preferably 1 to 10, more preferably 2 to 6, from the viewpoints of surface activity and formability of molecular aggregates such as micelles. 2 or 4 is more preferable, and 2 is particularly preferable.
  • the hydrophilic group which the compound which concerns on this embodiment has is preferable that it is a group of the same structure from a viewpoint of stability of molecular assemblies, such as a micelle, and the ease of interface physical property control.
  • the functional group having the hydrophilic group may be the hydrophilic group itself or a group in which the hydrophilic group is bonded to the linking group that connects the aromatic ring and the hydrophilic group.
  • the compound according to this embodiment includes a functional group having the hydrophilic group, a hydrophilic group, the aromatic ring, and the hydrophilic group. It is preferably a group in which a linking group for linking a functional group is bonded. That is, the hydrophilic group is preferably not directly bonded to the aromatic ring from the viewpoints of expression of surface activity and interface physical property control.
  • the linking group for linking the aromatic ring and the hydrophilic group is not particularly limited, and is selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the group consisting of at least one kind of atom is preferable, the group consisting of a carbon atom and a hydrogen atom, or the group consisting of a carbon atom, a hydrogen atom and an oxygen atom is more preferable.
  • the linking group may be linear, branched or a ring structure.
  • the linking group may be branched to have two or more hydrophilic groups.
  • the linking group may be a linking group that binds to two or more carbon atoms on the aromatic ring.
  • the number of carbon atoms of the linking group is not particularly limited, but is preferably 2 to 24 and preferably 2 to 18 from the viewpoint of surface activity in an aqueous medium and formability of molecular aggregates such as micelles. More preferably, 2 to 8 is more preferable, and 4 to 8 is particularly preferable. In addition, the number of carbon atoms of the linking group is preferably 2 to 24, more preferably 4 to 18, and more preferably 8 to 8 from the viewpoints of surface activity in a nonpolar solvent and formability of molecular aggregates such as reverse micelles. 18 is more preferred.
  • the linking group is preferably an alkylene group or a group containing one or more alkylene groups and one or more ether bonds, and more preferably an alkyleneoxy group.
  • the length of the linking group (the number of atoms connecting the aromatic ring and the hydrophilic group at the shortest) is the surface activity in an aqueous medium, and the viewpoint of the formation of molecular aggregates such as micelles. Therefore, 2 to 24 are preferable, 2 to 18 are more preferable, 2 to 8 are further preferable, and 4 to 8 are particularly preferable.
  • the length of the linking group is preferably 2 to 24, more preferably 4 to 18, more preferably 8 to 8 from the viewpoint of the surface activity in a nonpolar solvent and the formability of molecular aggregates such as reverse micelles. 18 is more preferred.
  • the compound according to this embodiment has an aromatic ring bonded to the 2, 4, and 5 positions of each imidazole ring in the hexaarylbisimidazole structure. You may have another substituent other than the functional group which has.
  • substituents include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, amide groups, acyloxy groups, amino groups, alkylamino groups, arylamino groups, dialkylamino groups, Examples include a diarylamino group, an alkylarylamino group, an alkylthio group, an arylthio group, a hydroxy group, and a mercapto group. Further, these substituents may be further substituted with the above substituents.
  • the compound according to this embodiment is preferably a compound represented by the following formula (1).
  • each R ion independently represents an ionic group
  • each L independently represents a single bond or a divalent linking group
  • each X ion independently represents a counter ion
  • R 1 and R 2 each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, a linear or branched alkyl group which may have a substituent, or a substituent.
  • a cycloalkyl group, a linear or branched alkenyl group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, a substituent represents a linear or branched alkyloxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted aromatic heterocyclic group which may have a group
  • p is independently 0
  • the sum of two p's The total is 1 or more
  • R each independently represents an integer of 0-5.
  • the ionic group of R ion in formula (1) is preferably a cationic group, an anionic group, or a zwitterionic group, and more preferably a cationic group or an anionic group.
  • the cationic group, the anionic group and the zwitterionic group have the same meanings as the above-described cationic group, anionic group and zwitterionic group, and preferred embodiments are also the same.
  • each R ion is preferably independently a quaternary ammonium group, more preferably a trialkylammonium group, still more preferably a trimethylammonium group or a triethylammonium group, and particularly preferably a trimethylammonium group.
  • the counter ion of X ion in formula (1) has the same meaning as the counter ion described above, and the preferred embodiment is also the same.
  • X ions are preferably each independently a monovalent anion, more preferably a chloride ion (Cl ⁇ ), a bromide ion (Br ⁇ ), or an alkali metal ion.
  • the ionic group is a zwitterionic group such as a betaine structure
  • X ion may not exist.
  • the number of X ions is a number corresponding to appropriate neutralization of the entire compound as appropriate.
  • L in Formula (1) is preferably a divalent linking group that imparts hydrophobicity from the viewpoint of surface activity and the ability to form molecular aggregates such as micelles.
  • the divalent linking group imparting hydrophobicity from the viewpoint of surface activity and the formation of molecular aggregates such as micelles, carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms It is preferably a group consisting of at least one kind of atom selected from the group consisting of, more preferably a group consisting of a carbon atom and a hydrogen atom, or more preferably a group consisting of a carbon atom, a hydrogen atom and an oxygen atom, An alkylene group or a group containing one or more alkylene groups and one or more ether bonds is more preferred, and an alkyleneoxy group is particularly preferred.
  • the divalent linking group may be linear, branched or a ring structure.
  • the number of carbon atoms of L in the formula (1) is preferably 2 to 18, and preferably 2 to 8, from the viewpoints of surface activity in an aqueous medium and formability of molecular aggregates such as micelles. More preferably, it is 4-8.
  • the number of carbon atoms of L in the formula (1) is preferably 4 to 18 from the viewpoint of the surface activity in a nonpolar solvent and the formability of molecular aggregates such as reverse micelles, and 8 to 18 It is more preferable that Furthermore, it is preferable that L in Formula (1) is the same group.
  • the length of L (the number of atoms connecting the aromatic ring and the ionic group in the shortest) is from the viewpoint of the surface activity in an aqueous medium and the formability of molecular aggregates such as micelles. 2 to 24 are preferred, 2 to 18 are more preferred, 2 to 8 are still more preferred, and 4 to 8 are particularly preferred.
  • the length of L is preferably 2 to 24, more preferably 4 to 18, more preferably 8 to 18 from the viewpoints of surface activity in a non-polar solvent and formability of molecular aggregates such as reverse micelles. Is more preferable.
  • R 1 and R 2 in Formula (1) are each independently preferably a halogen atom, an alkyl group, or an aryl group, more preferably a halogen atom or an alkyl group, and still more preferably an alkyl group.
  • each p independently represents an integer of 0 to 5, and the sum of the two p is 1 or more. That is, any one of the two p is an integer of 1 or more.
  • each p in formula (1) is preferably an integer of 1 to 3, preferably 1 or 2, from the viewpoints of surface activity and formability of molecular aggregates such as micelles. More preferably, it is particularly preferably 1 each (total 2).
  • Each q in formula (1) is preferably independently an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • each r is independently preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0.
  • At least two R 1, R 1 is preferably either the same group, if having two or more R 2, R 2 is either the same group It is preferable.
  • two or more p in Formula (1) are the same values, and the same applies to q and r.
  • the compound according to this embodiment is more preferably a compound represented by the following formula (2).
  • R al each independently represents an alkyl group
  • L 1 independently represents an alkylene group
  • Z 1 each independently represents a single bond, an oxygen atom, NR 3 , or a sulfur atom
  • R 3 represents a hydrogen atom, an alkyl group, or an aryl group
  • X 2 — each independently represents a counter anion.
  • R 1, R 2, and r in formula (2) has the same meaning as R 1, R 2, and r in Formula (1), a preferable embodiment thereof is also the same.
  • R al each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms, which may have a substituent, and more preferably an alkyl group having 1 to 4 carbon atoms. Further, a linear alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable. Moreover, it is preferable that all Ral in Formula (2) is the same group.
  • each L 1 is independently preferably an alkylene group having 2 to 18 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and still more preferably an alkylene group having 4 to 8 carbon atoms.
  • the alkylene group may be a linear alkylene group or a branched alkylene group.
  • L 1 in the formula (2) is preferably either the same group.
  • the length of L 1 (the number of atoms connecting the aromatic ring and the ionic group in the shortest) is the viewpoint of the surface activity in an aqueous medium and the formability of molecular aggregates such as micelles.
  • the length of L 1 is preferably from 4 to 18, more preferably from 8 to 18, from the viewpoints of surface activity in a nonpolar solvent and formability of molecular aggregates such as reverse micelles.
  • Z 1 in formula (2) is preferably each independently a single bond or an oxygen atom. Further, Z 1 in the formula (2) is preferably either the same group.
  • R 3 in the NR 3 is a hydrogen atom or an alkyl group, more preferably an alkyl group, more preferably an alkyl group having 1-8 carbon atoms.
  • X ⁇ in the formula (2) is independently preferably a monovalent anion, more preferably a chloride ion (Cl ⁇ ) or a bromide ion (Br ⁇ ). Further, X ⁇ in the formula (2) is preferably the same anion.
  • Each q in the formula (2) is preferably independently an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0. Moreover, it is preferable that q in Formula (2) is the same value.
  • the compound according to this embodiment is more preferably a compound represented by the following formula (3).
  • L 2 independently represents an alkylene group having 2 to 18 carbon atoms
  • R 4 and R 5 each independently represents a halogen atom or an alkyl group.
  • R al in formula (3), X -, q and r, R al in formula (2), X -, is synonymous with q and r, preferable embodiments thereof are also the same.
  • L 2 in formula (3) is each independently preferably an alkylene group having 2 to 8 carbon atoms from the viewpoint of surface activity in an aqueous medium and formability of molecular aggregates such as micelles.
  • a linear alkylene group having 8 is more preferable, and a linear alkylene group having 4 to 8 carbon atoms is still more preferable.
  • each L 2 in the formula (3) is independently preferably an alkylene group having 4 to 18 carbon atoms from the viewpoint of the surface activity in a nonpolar solvent and the formability of molecular aggregates such as reverse micelles, An alkylene group having 8 to 18 carbon atoms is more preferable, and a linear alkylene group having 8 to 18 carbon atoms is still more preferable.
  • R 4 and R 5 in Formula (3) are each independently preferably a linear or branched alkyl group which may have a substituent, more preferably an alkyl group having 1 to 8 carbon atoms, More preferred are 1-4 alkyl groups. Further, in the equation (3), if having two or more R 4, R 4 is preferably either the same group, if having two or more R 5, R 5 is either the same group It is preferable.
  • the compound according to this embodiment is more preferably a compound represented by the following formula (4).
  • R an each independently represents an anionic group
  • L an each independently represents an alkylene group, or two or more groups selected from the group consisting of an alkylene group, an ester bond and an ether bond
  • Z an represents each independently a single bond, an oxygen atom, NR 3 , or a sulfur atom
  • R 3 represents a hydrogen atom, an alkyl group, or an aryl group
  • X an + represents Each independently represents a counter cation.
  • R 1, R 2, and r in formula (4) has the same meaning as R 1, R 2, and r in Formula (1), a preferable embodiment thereof is also the same.
  • R an in formula (4) is preferably independently a carboxylate group, a sulfonate group, a phosphonate group, or a sulfate anion group (sulfate group), more preferably a carboxylate group or a sulfonate group. Further, R an in the formula (4) is preferably the same group.
  • L an in Formula (4) is preferably a group in which two or more groups selected from the group consisting of an alkylene group, an ester bond, and an ether bond are combined, and preferably three or more alkylene groups, one or more ester bonds, and A group in combination with one or more ether bonds is more preferred.
  • the number of carbon atoms in Lan in formula (4) is preferably independently 2 to 20, more preferably 4 to 10, and particularly preferably 5 to 12.
  • the alkylene group may be a linear alkylene group or a branched alkylene group.
  • L an is preferably the same group.
  • the length of Lan (the number of atoms connecting the aromatic ring and the ionic group at the shortest) is the viewpoint of the surface activity in an aqueous medium and the formability of molecular aggregates such as micelles.
  • the length of L 1 is preferably from 4 to 18, more preferably from 8 to 18, from the viewpoints of surface activity in a nonpolar solvent and formability of molecular aggregates such as reverse micelles.
  • Z an in Formula (4) is preferably each independently a single bond or an oxygen atom. Moreover, it is preferable that all Z an in Formula (4) is the same group.
  • R 3 in the NR 3 is a hydrogen atom or an alkyl group, more preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms.
  • X an + in formula (4) is preferably independently a monovalent cation, more preferably an alkali metal cation or a quaternary ammonium cation, and still more preferably an alkali metal cation. Further, X an + in formula (4) is preferably the same cation.
  • Each q in the formula (4) is preferably independently an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0. Moreover, it is preferable that q in Formula (4) is the same value.
  • the compound according to this embodiment is preferably a compound represented by the following formula (5).
  • R no independently represents a group having a nonionic hydrophilic group
  • R n1 and R n2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a substituent.
  • Linear or branched alkyl group which may have, cycloalkyl group which may have substituent, linear or branched alkenyl group which may have substituent, substituent
  • a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, a linear or branched alkyloxy group which may have a substituent, a substituted or unsubstituted aryl
  • np independently represents an integer of 0 to 5; the sum of two np is 1 or more;
  • np + nq in np and nq represents the number of groups bonded to one benzene ring is an integer of 1 ⁇ 5
  • nr each independently represents an integer of 0-5.
  • the group having a nonionic hydrophilic group of R no in formula (5) is preferably a group having a polyalkyleneoxy structure, a group having two or more hydroxy groups and an ester structure, or a group having an alkanolamide structure.
  • the polyalkyleneoxy structure and the number of repetitions thereof in the group having a polyalkyleneoxy structure of R no in formula (5) are the same as the above-described alkyleneoxy structure and the number of repetitions thereof, and preferred embodiments are also the same.
  • one terminal in the group having a polyalkyleneoxy structure of R no in formula (5) is an alkoxy group or a hydroxy group, more preferably an alkoxy group, and a methoxy group or an ethoxy group. It is particularly preferred.
  • R no in formula (5) is preferably independently an alkoxy polyalkyleneoxy group or a hydroxy polyalkyleneoxy group, more preferably an alkoxy polyethyleneoxy group or a hydroxy polyethyleneoxy group, and an alkoxy polyethyleneoxy group. It is particularly preferred.
  • the carbon number of R no in the formula (5) is preferably 5 or more, 20 or less, more preferably 5 or more and 18 or less, and particularly preferably 6 or more and 12 or less.
  • R n1 , R n2 and np in the formula (5) have the same meanings as R 1 , R 2 and p in the formula (1), and preferred embodiments are also the same.
  • each nq is preferably independently an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • each nr is independently preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0.
  • R n1 is preferably either the same group, if having two or more R n2, R n2 are both in the same group It is preferable.
  • two or more np in the formula (5) have the same value, and the same applies to nq and nr.
  • the compound according to the present embodiment exhibits photochromism and light controllability of interfacial physical properties, optical memory, sensor material (UV sensor), light control material (window glass, sunglasses), cosmetic material, printing ink (aqueous ink, UV ink) Etc.), drugs (chemicals, fragrances, colorants, etc.) release agents, controlled release materials, UV detectors, hydrogels, paints, fragrances, cosmetics such as nail polish and sunscreen agents, writing instruments, stationery, piping resistance control It is suitably used for various applications such as an agent.
  • composition is a composition including the compound according to the present embodiment, and is preferably a composition including the compound according to the present embodiment and an aqueous medium.
  • aqueous medium include water and a water-soluble organic solvent.
  • the water is not particularly limited, and ion-exchanged water, ultrapure water, distilled water, ultrafiltered water, tap water, hard water, soft water, and the like are used. In particular, contamination of impurities or generation of microorganisms is prevented. From this viewpoint, ion-exchanged water, ultrapure water, distilled water, and ultrafiltrated water are preferable.
  • water-soluble organic solvent examples include alcohols, nitrogen-containing solvents, sulfur-containing solvents, and carbonic acid esters. Among these, alcohols are preferable, and methanol, ethanol, isopropyl alcohol, and the like can be given. Water and the water-soluble organic solvent may be used alone or in combination of two or more. Moreover, when forming molecular aggregates, such as the reverse micelle mentioned above, it is preferable that the composition which concerns on this embodiment contains a nonpolar organic solvent. There is no restriction
  • the composition according to the present embodiment may include one type of compound according to the present embodiment alone, or may include two or more types.
  • the concentration of the compound according to this embodiment is not particularly limited, but is preferably 0.01 mM or more and 0.5 M or less.
  • the unit M of concentration represents mol / L.
  • composition according to this embodiment may contain components other than those described above.
  • additives include a surfactant other than the compound according to the present embodiment, a colorant, and an organic solvent other than those described above.
  • the photochromic material according to the present embodiment includes the compound according to the present embodiment.
  • the interfacial physical property light control agent according to the present embodiment includes the compound according to the present embodiment.
  • the photochromic material according to the present embodiment and the interfacial physical property light control agent according to the present embodiment can be used for various applications as described above in the compound according to the present embodiment.
  • the photochromic material according to this embodiment and the interfacial physical property light control agent according to this embodiment may include the compound according to this embodiment alone or in combination of two or more.
  • the content of the compound and the state of the compound (solution, solid, etc.) according to this embodiment in the photochromic material according to this embodiment and the interfacial physical property light control agent according to this embodiment are not particularly limited, and are used. It may be appropriately selected depending on the case.
  • the photochromic material according to the present embodiment and the interfacial physical property light control agent according to the present embodiment can further contain a known compound as necessary.
  • Specific examples of the photochromic material according to the present embodiment include sunglasses including the compound according to the present embodiment in a lens. When irradiated with ultraviolet rays, the optical density of the lens increases.
  • sunglasses with high optical transparency of the lens can be considered.
  • Specific examples of the interfacial physical property light control agent according to this embodiment include ink containing the compound according to this embodiment. Ink that lowers the viscosity during ejection and increases the viscosity, drying speed, etc. on the recording medium depending on the presence or absence of ultraviolet irradiation.
  • N-C6-LPD photochromic compound
  • N-C6-LPD A novel compound having a quaternary ammonium salt structure introduced as an ionic group was synthesized according to the above scheme.
  • 1,6-dibromohexane was introduced into 4-hydroxybenzaldehyde in a solvent of acetone (Acetone) in the presence of potassium carbonate (K 2 CO 3 ) using Williamson ether synthesis.
  • the compound obtained in (1) was reacted with benzyl in an acetic acid solvent in the presence of ammonium acetate (NH 4 OAc) to synthesize a lophine compound into which a bromo group was introduced.
  • NH 4 OAc ammonium acetate
  • Step 3 the lophine compound obtained in Step 2 is dimerized in water / dichloromethane (DCM) solvent in the presence of potassium ferricyanide (K 3 [Fe (CN) 6 ]) and sodium hydroxide.
  • Step 4 the dimer obtained in Step 3 is reacted with trimethylamine (N (CH 3 ) 3 ) in an acetone solvent, and a quaternary ammonium salt structure is introduced as an ionic group. N-C6-LPD) was obtained. It was confirmed by 1 H-NMR and mass spectrometry that the target substance in each step was obtained.
  • the synthesized N-C6-LPD was dissolved in water to a concentration of 5 mM under an argon (Ar) atmosphere, and this was irradiated with ultraviolet light using a mercury / xenon lamp. Discolored instantly. When the ultraviolet light was cut off, the color of the solution immediately returned to the original light yellow color.
  • FIG. 1 shows ultraviolet and visible absorption spectra of a 5 mM aqueous solution of N—C6-LPD before and after irradiation with ultraviolet light.
  • a peak near 470 nm and an increase in absorbance near 620 nm, which are characteristic of lofil radicals were observed by ultraviolet light irradiation. From these results, it was found that the lphine dimer structure of N—C6-LPD was cleaved by irradiation with ultraviolet light, and a lophyll radical was generated to cause coloring.
  • FIG. 2 shows the change with time of the absorbance at 620 nm with ultraviolet light irradiation.
  • the absorbance increased when irradiated with ultraviolet light, and the absorbance decreased immediately after the irradiation with ultraviolet light was stopped, suggesting that the dissociation / recombination reaction proceeds at high speed.
  • the reaction rate constant in the recombination reaction of the lophyll radical was determined.
  • apparent second-order rate constants were calculated using absorbance instead of concentration. The results are summarized in Table 1.
  • N—C6-LPD aqueous solution was 0.11 Abs ⁇ 1 ⁇ min ⁇ 1 in the normal lophine dimer (Octane) in the octane solvent, whereas N—C6— It was found that a 5 mM aqueous solution of LPD (N-C6-LPD aq.) was about 7.4 ⁇ 10 3 Abs ⁇ 1 ⁇ min ⁇ 1 and about 10 5 times faster. Further, if the conventional surfactants were dissolved N-C6-LPD in micelles formed (CTAB micellar aq.) And the speed 10 3 times more than was improved.
  • N—C6-LPD itself formed a molecular assembly to suppress the diffusion of radical species.
  • the molecular structure changes greatly, and as a result, changes in the shape of molecular aggregates (micelles) formed by surfactants are induced at high speed along with changes in color. It is considered that high-speed light control of physical properties has been achieved.
  • the synthesized TEG-LPD was dissolved in water to a concentration of 5 mM under an argon (Ar) atmosphere and irradiated with ultraviolet light using a mercury / xenon lamp.
  • the solution color instantly changed from pale yellow to blue. Discolored. When the ultraviolet light was cut off, the color of the solution immediately returned to the original light yellow color.
  • a novel compound (Anionic-LPD) having a carboxylate structure introduced as an ionic group was synthesized according to the above scheme.
  • Step 1 the hydroxy group of 4-hydroxybenzaldehyde is etherified with 2-bromoethanol.
  • Step 2 the compound obtained in Step 1 is subjected to an acetic acid (Acetic acid) solvent in the presence of ammonium acetate (NH 4 OAc). Among them, benzyl was reacted to synthesize a lophine compound. Further, in step 3, the lophine compound obtained in step 2 is dissolved in water / dichloromethane (CH 2 Cl 2 ) in the presence of potassium ferricyanide (K 3 [Fe (CN) 6 ]) and sodium hydroxide.
  • step 4 diglycolic anhydride (1,4-dioxane-2,6-dione) is reacted with the dimer obtained in step 3 to introduce a carboxylate structure as an ionic group.
  • the target substance (Anionic-LPD) was obtained. It was confirmed by 1 H-NMR and mass spectrometry that the target substance in each step was obtained.
  • the synthesized Anionic-LPD was dissolved in water to a concentration of 5 mM under an argon (Ar) atmosphere, and this was irradiated with ultraviolet light using a mercury / xenon lamp. The color of the solution instantly changed from pale yellow to blue. Discolored. When the ultraviolet light was cut off, the color of the solution immediately returned to the original light yellow color.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Le composé selon un mode de réalisation de l'invention a une structure d'hexaaryl-bisimidazole et a au moins un groupe fonctionnel avec un groupe hydrophile sur au moins un cycle aromatique qui est lié à un cycle imidazole de la structure d'hexaaryl-bisimidazole. La composition, le matériau photochromique ou l'agent de lutte contre les propriétés interfaciales selon les autres modes de réalisation de l'invention comprennent le composé selon le mode de réalisation de l'invention.
PCT/JP2017/030994 2016-09-07 2017-08-29 Nouveau composé, composition, matériau photochromique et agent de contrôle de propriété photo-interfaciale WO2018047681A1 (fr)

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JP7472438B2 (ja) 2019-06-20 2024-04-23 Dic株式会社 イミダゾール化合物

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